Abstract:

Fungicidal mixtures, comprising (1) epoxiconazole of the formula I
##STR00001## or its salts or adducts and (2) triticonazole of the
formula II
##STR00002## (3) difenconazole of the formula III
##STR00003## (4) hexaconazole of the formula IV
##STR00004## (5) bromuconazole of the formula V
##STR00005##
in a synergistically effective amount, methods for controlling harmful
fungi using mixtures of a compound I and at least one active compound II
and the use of a compound I with active compounds II for preparing such
mixtures, and also compositions comprising these mixtures.

Claims:

1. A fungicidal mixture, comprising(1) epoxiconazole of the formula I
##STR00016## or its salts or adductsand at least one further triazole or
its salts or adducts, selected from the group consisting of(2)
triticonazole of the formula II ##STR00017## (3) difenconazole of the
formula III ##STR00018## (4) hexaconazole of the formula IV ##STR00019##
(5) bromuconazole of the formula V ##STR00020## in a synergistically
effective amount.

2. The fungicidal mixture according to claim 1, comprising epoxiconazole
of the formula I and triticonazole of the formula II.

3. The fungicidal mixture according to claim 1, comprising epoxiconazole
of the formula I and difenconazole of the formula III.

4. The fungicidal mixture according to claim 1, comprising epoxiconazole
of the formula I and hexaconazole of the formula IV.

5. The fungicidal mixture according to claim 1, comprising epoxiconazole
of the formula I and bromuconazole of the formula V.

6. The fungicidal mixture according to claim 1, wherein the weight ratio
of epoxiconazole of the formula I to the respective triazole of the
formulae II to V is from 100:1 to 1:100.

7. A method for controlling harmful fungi, which comprises treating the
harmful fungi, their habitat or the plants, seeds, soils, areas,
materials or spaces to be kept free from them with the fungicidal mixture
according to claim 1.

8. The method according to claim 7, wherein the compound of the formula I
according to claim 1 and at least one compound of the formulae II to IV
according to claim 1 are applied simultaneously, that is jointly or
separately, or in succession.

9. The method according to claim 7 or 8, wherein the fungicidal mixture or
the compound of the formula I and at least one compound of the formulae
II to V according to claim 1 is/are applied in an amount of from 5 g/ha
to 2000 g/ha.

10. The method according to claim 7 or 8, wherein the compound I and at
least one of the compounds II to V according to claim 1 or the mixture
according to claim 1 are/is applied in an amount of from 1 g to 1000 g
per 100 kg of seed.

11. Seed, comprising the mixture according to claim 1 in an amount of from
1 g to 1000 g per 100 kg.

12. The use of the compound I and at least one of the compounds II to V
according to claim 1 for preparing a composition suitable for controlling
harmful fungi.

13. A fungicidal composition, comprising the fungicidal mixture according
to claim 1 and a solid or liquid carrier.

Description:

[0002]or its salts or adducts [0003]and(2) triticonazole of the formula II

##STR00007##

[0003](3) difenconazole of the formula III

##STR00008##

(4) hexaconazole of the formula IV

##STR00009##

(5) bromuconazole of the formula V

##STR00010##

in a synergistically effective amount.

[0004]Moreover, the invention relates to a method for controlling harmful
fungi using mixtures of the compound I with at least one of the compounds
II to V and to the use of the compound I with at least one of the
compounds II to V for preparing such mixtures, and also to compositions
comprising these mixtures.

[0005]A number of active compound combinations of prothioconazole with a
large number of other triazoles such as epoxiconazole is known from WO
03/073851.

[0006]Epoxiconazole of the formula I and its use as crop protection agent
are described in EP-B 0 196 038.

[0007]Triticonazole of the formula II is described in EP-A 0 378 953.

[0008]Difenconazole of the formula III is known from EP-A 0 112 284.

[0009]Hexaconazole of the formula IV is described in DE-A 30 42 303.

[0010]Bromuconazole of the formula V is described in Pesticide Manual,
12th Ed. (2000), page 114.

[0011]It is an object of the present inventions, with a view to reducing
the application rates and broadening the activity spectrum of the known
compounds, to provide mixtures which, at a reduced total amount of active
compounds applied, exhibit improved activity against harmful fungi, in
particular for specific indications.

[0012]We have found that this object is achieved by the mixtures defined
at the outset. Moreover, we have found that simultaneous, that is joint
or separate, application of the compounds I and an active compound II or
successive application of the compounds I and an active compound II
allows better control of harmful fungi than is possible with the
individual compounds (synergistic mixtures). The compounds I can be used
as synergist for a large number of different active compounds. By
simultaneous joint or separate application of the compound I and an
active compound II, the fungicidal efficacy is increased in a
superadditive manner.

[0013]Epoxiconazole of the formula I

##STR00011##

is known from EP-B 0 196 038.

[0014]Triticonazole of the formula II

##STR00012##

is described in EP-A 0 378 953.

[0015]Difenconazole of the formula III

##STR00013##

is described in EP-A 0 112 284.

[0016]Hexaconazole of the formula IV

##STR00014##

is described in DE-A 30 42 303.

[0017]Bromuconazole of the formula V

##STR00015##

is described in Pesticide Manual, 12th Ed. (2000), page 114.

[0018]Owing to the basic character of their nitrogen atoms, the compounds
I to V are capable of forming salts or adducts with inorganic or organic
acids and with metal ions, respectively.

[0021]Suitable metal ions are in particular the ions of the elements of
the second main group, in particular calcium and magnesium, of the third
and fourth main group, in particular aluminum, tin and lead and also of
the elements of transition groups one to eight, in particular chromium,
manganese, iron, cobalt, nickel, copper, zinc, and others. Particular
preference is given to the metal ions of the elements of transition
groups of the fourth period. The metals can be present in the various
valencies that they can assume.

[0022]Preference is given to mixtures of epoxiconazole with triticonazole.

[0023]Preference is furthermore given to mixtures of epoxiconazole with
difenconazole.

[0024]Preference is also given to mixtures of epoxiconazole with
hexaconazole.

[0025]Preference is furthermore given to mixtures of epoxiconazole with
bromuconazole.

[0026]The mixtures of the compound I and an active compound II, or the
compound I and an active compound II applied simultaneously, that is
jointly or separately, have excellent activity against a broad spectrum
of phytopathogenic fungi, in particular from the classes of the
Ascomycetes, Deuteromycetes, Peronosporomycetes (syn. Oomycetes) and
Basidiomycetes. Some of them are systemically effective and can be
employed in crop protection as fungicides for seed dressing, as foliar
fungicides and as soil fungicides.

[0027]They are of particular importance for the control of a large number
of fungi on various crop plants such as bananas, cotton, vegetable
species (for example cucumbers, beans and cucurbits), barley, grass,
oats, coffee, potatoes, corn, fruit plants, rice, rye, soybeans,
tomatoes, grapevines, wheat, ornamental plants, sugar cane and a large
number of seeds.

[0028]They are especially suitable for controlling the following plant
diseases: [0029]Alternaria species on vegetable species, oilseed rape,
sugar beet and fruit and rice, such as, for example, A. solani or A.
alternata on potatoes and tomatoes, [0030]Aphanomyces species on sugar
beet and vegetable species, [0031]Ascochyta species on cereals and
vegetable species, [0032]Bipolaris and Drechslera species on corn,
cereals, rice and lawn, such as, for example, D. maydis on corn, Blumeria
graminis (powdery mildew) on cereals, [0033]Botrytis cinerea (gray mold)
on strawberries, vegetable species, flowers and grapevines, [0034]Bremia
lactucae on lettuce, [0035]Cercospora species on corn, soybeans, rice and
sugar beet, [0036]Cochliobolus species on corn, cereals, rice, such as,
for example, Cochliobolus sativus on cereals, Cochliobolus miyabeanus on
rice, [0037]Colletotricum species on soybeans and cotton,
[0038]Drechslera species, Pyrenophora species on corn, cereals, rice and
lawn, such as, for example, D. teres on barley or D. tritici-repentis on
wheat, [0039]Esca on grapevines, caused by Phaeoacremonium
chlamydosporium, Ph. Aleophilum, and Formitipora punctata (syn. Phellinus
punctatus), [0040]Elsinoe ampelina on grapevines, [0041]Exserohilum
species on corn,

[0042]Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumber
species, [0043]Fusarium and Verticillium species on various plants,
such as, for example, F. graminearum or F. culmorum on cereals or F.
oxysporum on a large number of plants, such as, for example, tomatoes,
[0044]Gaeumanomyces graminis on cereals, [0045]Gibberella species on
cereals and rice (for example Gibberella fujikuroi on rice),
[0046]Glomerella cingulata on grapevines and other plants,
[0047]Grainstaining complex on rice, [0048]Guignardia budwelli on
grapevines, [0049]Helminthosporium species on corn and rice,
[0050]Isariopsis clavispora on grapevines, [0051]Michrodochium nivale on
cereals, [0052]Mycosphaerella species on cereals, bananas and peanuts,
such as, for example, M. graminicola on wheat or M. fijiensis on bananas,
[0053]Peronospora species on cabbage and bulbous plants, such as, for
example, P. brassicae on cabbage or P. destructor on onion,
[0054]Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans,
[0055]Phomopsis species on soybeans and sunflowers, P. viticola on
grapevines, [0056]Phytophthora infestans on potatoes and tomatoes,
[0057]Phytophthora species on various plants, such as, for example, P.
capsici on bellpeppers, [0058]Plasmopara viticola on grapevines,
[0059]Podosphaera leucotricha on apple, [0060]Pseudocercosporella
herpotrichoides on cereals, [0061]Pseudoperonospora on various plants,
such as, for example, P. cubensis on cucumber or P. humili on hops,
[0062]Pseudopezicula tracheiphilai on grapevines, [0063]Puccinia species
on various plants, such as, for example, P. triticina, P. striformins, P.
hordei or P. graminis on cereals, or P. asparagi on asparagus,
[0064]Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.
attenuatum, Entyloma oryzae on rice, [0065]Pyricularia grisea on lawn and
cereals,

[0066]Pythium spp. on lawn, rice, corn, cotton, oilseed rape, sunflowers,
sugar beet, vegetable species and other plants, such as, for example, P.
ultiumum on various plants, P. aphanidermatum on lawn,
[0067]Rhizoctonia species on cotton, rice, potatoes, lawn, corn, oilseed
rape, potatoes, sugar beet, vegetable species and on various plants, such
as, for example, R. solani on beets and various plants,
[0068]Rhynchosporium secalis on barley, rye and triticale,
[0069]Sclerotinia species on oilseed rape and sunflowers, [0070]Septoria
tritici and Stagonospora nodorum on wheat, [0071]Erysiphe (syn. Uncinula)
necator on grapevines, [0072]Setospaeria species on corn and lawn,
[0073]Sphacelotheca reilinia on corn, [0074]Thievaliopsis species on
soybeans and cotton, [0075]Tilletia species on cereals, [0076]Ustilago
species on cereals, corn and sugar cane, such as, for example, U. maydis
on corn, [0077]Venturia species (scab) on apples and pears, such as, for
example, V. inaequalis on apple.

[0078]The mixtures of the compounds I and an active compound II are
particularly suitable for controlling harmful fungi from the class of the
Peronosporomycetes (syn. Oomyceten), such as Peronospora species,
Phytophthora species, Plasmopara viticola and Pseudo-peronospora species,
in particular the corresponding species mentioned above.

[0080]The compounds I are applied by treating the fungi or the plants,
seed, materials or the soil to be protected against fungal attack with a
fungicidally effective amount of the active compounds. Application can be
both before and after the infection of the materials, plants or seeds by
the fungi.

[0081]The compounds I and active compounds II can be applied
simultaneously, that is jointly or separately, or in succession, the
sequence, in the case of separate application, generally not having any
effect on the result of the control measures.

[0082]When preparing the mixtures, it is preferred to employ the pure
active compounds I and at least one of the active compounds II to V, to
which further compounds active against harmful fungi or other pests, such
as insects, arachnids or nematodes, or else herbicidal or
growth-regulating active compounds or fertilizers can be added.

[0083]Usually, mixtures of compound I and at least one of the active
compounds II to V are employed. However, in certain cases mixtures of the
compound I with two or, if appropriate, more active components may also
be advantageous.

[0084]The compound I and the active compound II are usually employed in a
weight ratio of from 100:1 to 1:100, preferably from 20:1 to 1:20, in
particular from 10:1 to 1:10.

[0085]The compound I and the active compound III are usually employed in a
weight ratio of from 100:1 to 1:100, preferably from 20:1 to 1:20, in
particular from 10:1 to 1:10.

[0086]The compound I and the active compound IV are usually employed in a
weight ratio of from 100:1 to 1:100, preferably from 20:1 to 1:20, in
particular from 10:1 to 1:10.

[0087]The compound I and the active compound V are usually employed in a
weight ratio of from 100:1 to 1:100, preferably from 20:1 to 1:20, in
particular from 10:1 to 1:10.

[0088]The further active components are, if desired, added in a ratio of
from 20:1 to 1:20 to the compound I.

[0089]Depending on the type of compound and the desired effect, the
application rates of the mixtures according to the invention, especially
on agricultural crop areas, are from 5 g/ha to 2000 g/ha, preferably from
20 to 900 g/ha, in particular from 50 to 750 g/ha.

[0090]Correspondingly, the application rates for the compound I are
generally from 1 to 1000 g/ha, preferably from 10 to 900 g/ha, in
particular from 20 to 750 g/ha.

[0091]Correspondingly, the application rates for the active compound II
are generally from 1 to 2000 g/ha, preferably from 10 to 1500 g/ha, in
particular from 40 to 1000 g/ha.

[0092]Correspondingly, the application rates for the active compound III
are generally from 1 to 2000 g/ha, preferably from 10 to 1500 g/ha, in
particular from 40 to 1000 g/ha.

[0093]Correspondingly, the application rates for the active compound IV
are generally from 1 to 2000 g/ha, preferably from 10 to 1500 g/ha, in
particular from 40 to 1000 g/ha.

[0094]Correspondingly, the application rates for the active compound V are
generally from 1 to 2000 g/ha, preferably from 10 to 1500 g/ha, in
particular from 40 to 1000 g/ha.

[0095]In the treatment of seed, application rates of mixture used are
generally from 1 to 1000 g/100 kg of seed, preferably from 1 to 750 g/100
kg, in particular from 5 to 500 g/100 kg.

[0096]The method for controlling harmful fungi is carried out by the
separate or joint application of compound I and at least one of the
active compounds II to V or a mixture of compound I and at least one of
the active compounds II to V by spraying or dusting the seeds, the plants
or the soils before or after sowing of the plants or before or after
emergence of the plants.

[0097]The mixtures according to the invention, or the compound I and at
least one of the active compounds II to V can be converted into the
customary formulations, for example solutions, emulsions, suspensions,
dusts, powders, pastes and granules. The use form depends on the
particular intended purpose; in each case, it should ensure a fine and
even distribution of the compound according to the invention.

[0098]The formulations are prepared in a known manner, for example by
extending the active compound with solvents and/or carriers, if desired
using emulsifiers and dispersants.

[0105]In general, the formulations comprise from 0.01 to 95% by weight,
preferably from 0.1 to 90% by weight, of the active compounds. The active
compounds are employed in a purity of from 90% to 100%, preferably 95% to
100% (according to NMR spectrum).

[0106]The following are examples of formulations: 1. Products for dilution
with water

A) Water-Soluble Concentrates (SL)

[0107]10 parts by weight of a compound according to the invention are
dissolved in 90 parts by weight of water or in a water-soluble solvent.
As an alternative, wetting agents or other auxiliaries are added. The
active compound dissolves upon dilution with water. In this way, a
formulation having a content of 10% by weight of active compound is
obtained.

B) Dispersible Concentrates (DC)

[0108]20 parts by weight of a compound according to the invention are
dissolved in 70 parts by weight of cyclohexanone with addition of 10
parts by weight of a dispersant, for example polyvinylpyrrolidone.
Dilution with water gives a dispersion. The active compound content is
20% by weight.

C) Emulsifiable Concentrates (EC)

[0109]15 parts by weight of a compound according to the invention are
dissolved in 75 parts by weight of xylene with addition of calcium
dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts
by weight). Dilution with water gives an emulsion. The formulation has an
active compound content of 15% by weight.

D) Emulsions (EW, EO)

[0110]25 parts by weight of a compound according to the invention are
dissolved in 35 parts by weight of xylene with addition of calcium
dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts
by weight). This mixture is introduced into 30 parts by weight of water
by means of an emulsifying machine (e.g. Ultraturrax) and made into a
homogeneous emulsion. Dilution with water gives an emulsion. The
formulation has an active compound content of 25% by weight.

E) Suspensions (SC, OD)

[0111]In an agitated ball mill, 20 parts by weight of a compound according
to the invention are comminuted with addition of 10 parts by weight of
dispersants and wetting agents and 70 parts by weight of water or an
organic solvent to give a fine active compound suspension. Dilution with
water gives a stable suspension of the active compound. The active
compound content in the formulation is 20% by weight.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

[0112]50 parts by weight of a compound according to the invention are
ground finely with addition of 50 parts by weight of dispersants and
wetting agents and prepared as water-dispersible or water-soluble
granules by means of technical appliances (for example extrusion, spray
tower, fluidized bed). Dilution with water gives a stable dispersion or
solution of the active compound. The formulation has an active compound
content of 50% by weight.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP)

[0113]75 parts by weight of a compound according to the invention are
ground in a rotorstator mill with addition of 25 parts by weight of
dispersants, wetting agents and silica gel. Dilution with water gives a
stable dispersion or solution of the active compound. The active compound
content of the formulation is 75% by weight.

2. Products to be Applied Undiluted

H) Dustable Powders (DP)

[0114]5 parts by weight of a compound according to the invention are
ground finely and mixed intimately with 95 parts by weight of finely
divided kaolin. This gives a dustable product having an active compound
content of 5% by weight.

J) Granules (GR, FG, GG, MG)

[0115]0.5 part by weight of a compound according to the invention is
ground finely and associated with 99.5 parts by weight of carriers.
Current methods are extrusion, spraydrying or the fluidized bed. This
gives granules to be applied undiluted having an active compound content
of 0.5% by weight.

K) ULV Solutions (UL)

[0116]10 parts by weight of a compound according to the invention are
dissolved in 90 parts by weight of an, organic solvent, for example
xylene. This gives a product to be applied undiluted having an active
compound content of 10% by weight.

[0117]The active compounds can be used as such, in the form of their
formulations or the use forms prepared therefrom, for example in the form
of directly sprayable solutions, powders, suspensions or dispersions,
emulsions, oil dispersions, pastes, dustable products, materials for
spreading, or granules, by means of spraying, atomizing, dusting,
spreading or pouring. The use forms depend entirely on the intended
purposes; they are intended to ensure in each case the finest possible
distribution of the active compounds according to the invention.

[0118]Aqueous use forms can be prepared from emulsion concentrates, pastes
or wettable powders (sprayable powders, oil dispersions) by adding water.
To prepare emulsions, pastes or oil dispersions, the substances, as such
or dissolved in an oil or solvent, can be homogenized in water by means
of a wetting agent, tackifier, dispersant or emulsifier. However, it is
also possible to prepare concentrates composed of active substance,
wetting agent, tackifier, dispersant or emulsifier and, if appropriate,
solvent or oil, and such concentrates are suitable for dilution with
water.

[0119]The active compound concentrations in the ready-to-use preparations
can be varied within relatively wide ranges. In general, they are from
0.0001 to 10%, preferably from 0.01 to 1%.

[0120]The active compounds may also be used successfully in the
ultra-low-volume process (ULV), it being possible to apply formulations
comprising over 95% by weight of active compound, or even to apply the
active compound without additives.

[0121]Oils of various types, wetting agents or adjuvants may be added to
the active compounds, even, if appropriate, not until immediately prior
to use (tank mix). These agents are typically admixed with the
compositions according to the invention in a weight ratio of from 1:100
to 100:1, preferably from 1:10 to 10:1.

[0122]The compound I and at least one of the active compounds II to V, or
the mixtures or the corresponding formulations are applied by treating
the harmful fungi, the plants, seeds, soils, areas, materials or spaces
to be kept free from them with a fungicidally effective amount of the
mixture or, in the case of separate application, of the compound I and at
least one of the active compounds II to V. Application can be before or
after the infection by harmful fungi.

[0123]The fungicidal action of the individual compounds and of the
mixtures according to the invention was demonstrated by the tests below.

[0124]The efficacy (E) is calculated as follows using Abbot's formula:

E=(1-α/β)100

[0125]α corresponds to the fungicidal infection of the treated
plants in % and

β corresponds to the fungicidal infection of the untreated (control)
plants in %

[0126]An efficacy of 0 means that the infection level of the treated
plants corresponds to that of the untreated control plants; an efficacy
of 100 means that the treated plants are not infected.

E=x+y-xy/100 [0129]E expected efficacy, expressed in % of the untreated
control, when using the mixture of the active compounds A and B at the
concentrations a and b [0130]x efficacy, expressed in % of the untreated
control, when using the active compound A at the concentration a [0131]y
efficacy, expressed in % of the untreated control, when using the active
compound B at the concentration b

[0132]The active compound epoxiconazole and triticonzole was used as a
commercial formulation.

[0134]The stock solution is pipetted onto a microtiter plate (MTP) and
diluted to the stated active compound concentration using a malt-based
aqueous nutrient medium for fungi. An aqueous spore suspension of
Pyricularia oryzae was then added. The plates were placed in a water
vapor-saturated chamber at temperatures of 18° C. Using an
absorption photometer, the MTPs were measured at 405 nm on day 7 after
the inoculation. The measured parameters were compared to the growth of
the active compound-free control variant and the fungus- and active
compound-free blank value to determine the relative growth in % of the
pathogens in the individual active compounds.

[0135]The visually determined values for the percentage of infected leaf
area were initially converted into a mean value and then converted into
efficacies in % of the untreated control. An efficacy of 0 means the same
degree of infection as in the untreated control, an efficacy of 100 means
0% infection. The expected efficacies for active compound combinations
were determined using Colby's formula (Colby, S. R. "Calculating
synergistic and antagonistic responses of herbicide combinations", Weeds,
15, pp. 20-22, 1967) and compared to the observed efficacies.